JP4564980B2 - Method for removing sulfur from hydrocarbon liquids - Google Patents

Abstract

The present invention is directed to a method of desulfurization of a sulfur laden hydrocarbon liquid that comprises contacting the liquid with a sponge nickel metal alloy, removing the sulfur free liquid, regeneration of the alloy by contact with an aqueous solution of an oxidant and reusing the alloy for further desulfurization of additional sulfur laden liquid.

Description

The present invention is directed to an improved process that can provide a product stream of light and heavy gasoline fractions substantially free of sulfur-containing compounds.

Catalytic cracking is an oil refining process that has been applied commercially on a large scale. The majority of refined gasoline blend pools in the United States are manufactured using fluid catalytic cracking (FCC) processes. In this process, the heavy hydrocarbon feed is converted to a light product by a reaction that occurs at high temperatures in the presence of a catalyst, mostly occurring in the vapor phase. This converts this feed into gasoline, distillate and other liquid distillate product streams and light gaseous cracked products having up to 4 carbon atoms per molecule. The three characteristic stages of the catalytic cracking process are a cracking stage that converts the heavy hydrocarbon feed stream to a light product, a stripping stage that removes adsorbed hydrocarbons from the catalyst material, and a coke from the catalyst material. The product comprises a regeneration stage where the product is burned out and then recycled and reused in the cracking stage.

Petroleum feedstocks usually contain organic sulfur compounds such as mercaptans, sulfides and thiophenes. About half of this sulfur compound is converted to hydrogen sulfide during the cracking process, mainly by catalytic cracking of non-thiophene sulfur compounds, but the products of this cracking process tend to contain sulfur impurities accordingly. Thiophene-type and other organic sulfur-containing compounds have proven to be the most difficult to remove. The specific distribution of sulfur in the cracked product depends on a number of factors including feed, type of catalyst, additives present, conversion and other operating conditions, but in any case the proportion of this sulfur is There is a tendency to enter light or heavy gasoline fractions, and enter the product pool. Petroleum feedstocks usually contain various sulfur-based pollutants, but one of the main concerns is that thiophene in the heavy and light gasoline distillate product streams of the refining process (eg, fluid cracking catalytic process), The presence of unsubstituted and hydrocarbyl substituted thiophenes and their derivatives, such as methylthiophene, ethylthiophene, propylthiophene, benzothiophene, and tetrahydrothiophene, and thiophenol. These compounds generally have boiling points within the light and heavy gasoline fractions and thus become concentrated in these product streams.

In response to concerns about the release of sulfur oxides and other sulfur compounds into the atmosphere after combustion, various government agencies have issued regulations on the amount of sulfur contained in these petroleum refined products. For example, the US government issued reformed gasoline (RFG) regulations and amendments to the Air Pollution Control Act. In addition, the California Air Resources Board has set a limit for sulfur concentrations in gasoline of approximately 40 parts per million (ppm). Since the current sulfur level in gasoline is about 385 ppm, these low level new goals require significant measures for the majority of oil refiners to meet this new level.

Several approaches have been developed to remove sulfur from gasoline. One approach was to remove sulfur-containing compounds from this by hydrotreating the feed prior to decomposition. While very effective, this approach tends to be expensive in terms of operation as it consumes the required capital costs of the equipment as well as large amounts of hydrogen.

It is desirable from an economic point of view to remove thiophene-type sulfur in the cracking process itself as it effectively desulfurizes the major components of the gasoline blend pool without additional treatment.
Various catalyst materials have been developed for sulfur removal during FCC process cycles. For example, FCC catalysts impregnated with vanadium and nickel metal have been shown to reduce the amount of product sulfur. See (Non-Patent Document 1). This reference also showed that zinc-impregnated alumina-based sulfur reducing additives are effective in reducing product sulfur in FCC products. However, when these materials are mixed with a metal-impregnated FCC catalyst,
The impact of sulfur reduction has decreased and has become economically inefficient.

Other developments to reduce product sulfur center around the removal of sulfur from the regenerator flue gas. An early development developed by Chevron was the use of alumina compounds as an additive to the inventory of cracking catalysts to adsorb sulfur oxides in FCC regenerators; adsorbed sulfur entering the process in this feed The compound was released as hydrogen sulfide during the cracking portion of the cycle and was transferred to the product recovery section of the unit and removed. See (Non-Patent Document 2). Sulfur is removed from the flue gas of this regenerator, but the product sulfur level is not significantly affected.

An alternative technique for removing sulfur oxides from the regenerator flue gas is based on the use of magnesium-aluminum spinel as an additive to the inventory of circulating catalysts in the FCC unit. Exemplary patents disclosing this type of sulfur removal additive include (Patent Document 1), (Patent Document 2), (Patent Document 3), (Patent Document 4) and others. However, again, product sulfur levels are not significantly reduced.

Catalyst compositions that reduce the level of sulfur in liquid cracking products are described in (Patent Document 5) and (
Patent document 6). This composition proposes the addition of a cracking catalyst additive composed of an alumina-supported Lewis acid together with a conventional zeolite molecular sieve.
While this system has the advantage of causing sulfur reduction during the cracking process, the composition has not had significant commercial success. Even when high levels of this alumina-supported Lewis acid additive are included in this composition, the composition proposed by Wormsbecher et al. Proved not to result in a significant reduction in the levels of thiophene and its derivatives. did. The use of more than about 10 weight percent additive in these compositions does not provide a merit commensurate with the cost of this additive.

The possibility of adsorbing thiophene directly from gasoline was briefly discussed in the scientific literature. (Non-patent document 3) and (Non-patent document 4) showed that a certain zeolitic material can be used to adsorb thiophene from olefin-free gasoline. Exchange type zeolites such as Ag exchange type zeolite Y and Cu exchange type zeolite Y have been shown to adsorb sulfur from standard gasoline (see (Patent Document 7) and (Patent Document 8)). However, in each case, the absorption capacity of this adsorbent material is insufficient for commercial applications.

It has also been recognized that due to the presence of organic sulfur compounds in this fuel source, raw fuels such as gasoline, diesel fuel and the like may not be useful as fuel sources for fuel cell power plants. . Hydrogen production in the presence of sulfur and sulfur compounds has a poisoning effect on all catalysts used in hydrogenation production systems, including fuel cell anode catalysts. Conventional fuel processing systems used in fuel cell power generators include thermal steam reformers such as those described in US Pat. In such systems, sulfur is removed from the fuel by conventional hydrodesulfurization processes. The produced hydrogen sulfide is then removed using a zinc oxide bed. While this system is satisfactory when used in combination with large stationary applications, it is not suitable for mobile transportation applications due to the size, cost and complexity of the system. It is highly desirable to have a cost-effective means of removing sulfur from this so that the hydrocarbon fuel can be used in fuel cell applications.
US Pat. No. 4,963,520 U.S. Pat. No. 4,957,892 U.S. Pat. No. 4,957,718 U.S. Pat. No. 4,790,982 US Pat. No. 5,376,608 (Wormsbecher and Kim) US Pat. No. 5,525,210 U.S. Pat. No. 4,188,285 EP0,275,855 US Pat. No. 5,516,334 US Pat. No. 1,628,190 US Pat. No. 1,915,473 U.S. Pat. No. 2,139,602 U.S. Pat. No. 2,461,396 U.S. Pat. No. 2,977,327 US Pat. No. 4,826,799 U.S. Pat. No. 4,895,994 US Pat. No. 3,351,495 US Pat. No. 3,904,551 US Pat. No. 3,904,551 US Pat. No. 3,351,495 US Pat. No. 3,907,710 (Lundsager) US Pat. No. 4,510,263 (Pereira et al.) US Pat. No. 4,826,799 U.S. Pat. No. 4,895,994 Myrstad et al., “Effect of Nickel and Vanadium on Sulfur Reduction of FCC Naptha”, Applied Catalyst A: General 192 (2000) pages 299-305. Krishna et al., “Additives Improved FCC Process”, Hydrocarbon Processing, November 1991, pages 59-66. A. B. Salem, Ind. Eng. Chem. Res. , 33, page 336 (1964) Garcia et al. Phys. Chem. 96 page 2669 (1991) Freeel et al., Journal. of Catalysis, vol. 14, no. 3, p. 247 (1969) "Surfaces of Raney (R) Catalysts" by S.C. R. Schmidt in Catalysis of Organic Reactions, edited by Scaros and Prunier, published by M.M. Dekker (1995)

It would be desirable to have an economical and effective method that can remove sulfur-containing materials such as thiophene directly from the gasoline product stream obtained from the cracking process.

Selectively adsorb sulfur-containing material contained in a gasoline product stream, and the adsorbent easily desorbs and recycles the sulfur material to further remove sulfur material from further gasoline products. It is also desirable to have an economical and effective method that can be used.

The present invention involves contacting a sulfur-containing hydrocarbon liquid, such as a product stream liquid of a petroleum refining process, with a useful Raney ^(R) nickel catalyst composition in a packed bed reactor, and desulfurizing the hydrocarbon liquid from Raney nickel material. Directed to desulfurization of hydrocarbon compositions by separation. This method further provides for removing sulfur species from Raney nickel and reusing the regenerated catalyst to treat additional sulfur-containing hydrocarbon liquids.

The present method provides an effective and economical method for removing sulfur species from light and heavy gasoline fractions obtained from cracking hydrocarbon liquids, particularly petroleum heavy hydrocarbon feedstocks. The process comprises a porous nickel-containing product containing a sulfur-containing hydrocarbon liquid product in a fixed bed reactor.
Contacting with an alumina or nickel-aluminum fixed bed catalyst material and recovering the resulting desulfurized hydrocarbon liquid. The sulfur species of the sulfur-containing fixed bed catalyst can be easily removed by the present invention to obtain a regenerated porous catalyst. This catalyst can be used again to remove sulfur species from further hydrocarbon liquids. Thus, the present invention provides a method by which sulfur-free hydrocarbon products can be produced effectively and economically.

The terms “fixed bed reactor” or “packed bed reactor” are used in the specification and the claims appended hereto, as the catalyst is densely packed, or substantially Any reactor that exists in a fixed form refers interchangeably. For example, the reactor may have the form of a packed column or an ebullated bed. The terms “fixed bed catalyst” or “packed bed catalyst” refer interchangeably to catalyst compositions that are useful in these reactors.

The method and system of the present invention is particularly adapted for treating hydrocarbon product streams from catalytic cracking processes. However, it should be understood that the scope of the present invention is not limited to hydrocarbon liquids obtained from such processes.

The methods and systems of the present invention are also useful in the treatment of hydrocarbon product streams envisioned for use in fuel cell applications.

Catalytic cracking is an oil refining process that converts heavy hydrocarbon feedstocks to light products by reactions that occur at high temperatures in the presence of catalysts. This conversion occurs mostly in the vapor phase. This feed is converted to gasoline, distillate and other liquid products and light gaseous products having 1 to 4 carbon atoms per molecule. This petroleum refining process accumulated on the catalyst during the cracking stage to convert petroleum hydrocarbons to light, commercially desirable distillate products, stripping stage to remove hydrocarbons adsorbed on the catalyst, and cracking It is generally accepted that it consists of three stages comprising a regeneration stage in which coke is burned off.

A distillate product suitable for treatment according to the present invention is typically about 10 volume percent at about 80 °.
Has a boiling point in the range of ˜180 ° F. (27 ° -83 ° C.) and the remainder is about 180 ° to 500 °
It is a light product composed of hydrocarbon components having boiling points in the range of ° F (83 ° to 260 ° C). A suitable distillate product is about 10 volume percent about 300 ° F. (149 ° C.).
) To 500 ° F. (260 ° C.) and the remaining 90 volume percent is about 500
It may be a light cycle oil and / or gasoline product having a boiling point in the range of from ° F (260 ° C) to about 750 ° F (399 ° C).

A typical distillate that can be subjected to the desulfurization process of the present invention described below has the following characteristics.

This distillate hydrocarbon mixture usually contains sulfur species that need to be removed to provide a product with a reduced sulfur content that renders the product environmentally acceptable. This product stream may be a product from a hydrotreating process (hydrocracking and treated product) or an absorption process (treatment).

The terms “sulfur” and “sulfur species” as used herein and in the appended claims refer to elemental sulfur and organic sulfur compounds such as propyl sulfide, butyl sulfide, pentyl sulfide, hexyl sulfide, and the like. di _C 3 -C ₆ sulfide; for example ethyl disulfide, propyl disulfide, disulfides such as _di-C 2 -C ₄ disulfide and butyl disulfide; for example, methanethiol, ethanethiol, _C 1 -C ₄ alkanethiol, such as propanethiol etc. mercaptans; methylthiophene, ethylthiophene, propyl, thiophene, such as dihydrothiophene; e.g., Benzochio such C ₁ -C ₄ alkyl benzothiophenes such as methylbenzothiophene, dimethyl benzothiophene E emissions; dibenzothiophene; mixture of organic sulfur compounds contained in liquid hydrocarbons, it refers to those which include the like.

The present invention is directed to contacting a sulfur-containing hydrocarbon distillate with a sponge nickel metal alloy catalyst (also referred to herein as a “Raney nickel catalyst”). The distillate and Raney nickel may be contacted by passing the distillate through a packed bed (for example, a fixed bed or a boiling bed) of the catalyst of the present invention. This material is typically contacted under an ambient pressure that is between atmospheric and slightly pressurized (eg, up to about 5 atmospheres). This material is 15-15 ° C, such as 15 ° C to 70 ° C.
Contact is made at a temperature in the range of 50 ° C.

“Raney Ni”, as used herein and in the appended claims, refers to a nickel and aluminum porous catalyst alloy based material, which may further contain small amounts of other metals. Nickel is present in about 35-60 weight percent and the remainder is primarily aluminum, nickel and aluminum (sometimes other small amounts of Cr, Mo, Fe, Cu, Co, Zn, etc. up to about 10 weight percent) First forming a precursor alloy (with metal in it); exposing the formed alloy to an aqueous alkali (eg, sodium hydroxide) solution to extract aluminum metal from the alloy; A catalyst is formed. If the porous material produced is a coarse granular fixed bed type (cross-sectional diameter of about 2 to 6 mm), the aluminum is partially extracted to give about 60 to 40 weight percent, preferably 55 to 45 percent. Holds weight percent Ni and about 40-60 weight percent Al. This fine granular fixed bed type (about 0.1 to 2 mm cross-sectional diameter)
Typically, it has about 60 to 95 weight percent Ni and about 5 to 40 weight percent Al. As noted above, the small amount of porous catalyst produced may be composed of copper, iron, cobalt, zinc, chromium, molybdenum and mixtures thereof, and chemically bonded oxygen in the product species.

This Raney Ni material can be formed according to the methods described in (Patent Literature 10), (Patent Literature 11), (Patent Literature 12), (Patent Literature 13), and (Patent Literature 14). The teachings of these patents are incorporated herein by reference in their entirety. A commercial product of this material is W.W. R. Grace & Co. Sold under the trademark RANEY®.

The catalyst material is (a) granular; (b) a polymer binder that does not undergo calcination; or (c
) It may be a calcined product. When the catalyst is a formed material (b) or (c), the catalyst has a particle size in the range of minus 50 mesh (US standard sieve) or less, such as minus 100 mesh or more preferably minus 200 mesh. It is formed from Raney Ni particles. The term “minus”, when used in conjunction with the mesh size, refers to material that passes through the indicated mesh sieve (US standard sieve). Raney Ni catalysts are incorporated herein by reference in their entirety, (US Pat. Nos. 5,099,049) and (6,097).
May be formed by conventional methods such as those described in. For example, the catalyst involved in contacting the fixed or moving bed of the packed bed catalyst with a sulfur containing hydrocarbon liquid may be formed by:
Nickel and aluminum alloy particles of minus 50 mesh or less are first mixed with the high molecular weight polymer alone or further with a plasticizer for this polymer such as mineral oil. in addition,
Small amounts (up to about 10% by weight) of other ingredients such as inert fillers, stabilizers, etc. can be added to the mixture.

This mixture is usually formed into a shaping material by extrusion and cutting or by pelletization.

The shaping material is then subjected to other process steps to remove all or at least most of the plasticizer from the extraction or shaping material.

The shaping material may then be processed in a manner that forms an active fixed bed catalyst. For example, this shaping material may be treated with an alkali (for example, sodium hydroxide) to remove aluminum metal by a conventional Raney method. Thus, the resulting material is Raney Ni having a shape bound by a polymer.

Alternatively, the shaped fixed bed catalyst material can be calcined and then subjected to an alkaline solution to remove most of the aluminum from the initial alloy. Generated porous shaped Raney Ni
Is substantially free of polymers and plasticizers.

As described above, the fixed bed catalyst can be molded using the polymer alone or additionally with a plasticizer of the polymer.

When this material is calcined, alkaline elution of aluminum from the calcined fixed bed catalyst precursor may result in a Raney Ni fixed bed catalyst, which is illustrated by the table below in this specification. What is being done. Oxygen may be present bonded to aluminum (as alumina), and in addition may be chemically bonded to other metals where a small amount of oxygen is present. This accounts for the difference in compositional content when performed on a metal-only basis versus that performed on an overall composition basis. Maintaining a high aluminum content as metal or alumina provides a high strength fixed bed catalyst suitable for cycle processing, which is required by the present invention and is described herein below. It is what.

The generalized compositions formed by various extrusion or pelletizing methods are shown in the table below.

Suitable polymers for the formation of fixed bed catalysts for use in the present invention include materials that are liquid at some stage of processing. Thermoplastic resins suitable for the practice of the present invention include unplasticized polyvinyl chloride, polyvinyl chloride-propylene copolymer, polyvinyl chloride-ethylene copolymer, polyvinylidene chloride copolymer, polystyrene, impact styrene, ABS resin, styrene butadiene. Block copolymers, polyethylene copolymers with low (specific gravity 0.91) to high density (specific gravity 0.97) polyethylene, propylene, butene, 1-pentene, 1-octene, hexene, styrene, vinyl acetate, alkyl acrylate, Polyethylene copolymer with sodium acrylate, acrylic acid, etc., chlorinated polyethylene, chlorosulfonated polyethylene, polypropylene and propylene-olefin copolymer, polybutene and butylene-olefin copolymer, poly-4-methyl-1 Pentene, thermoplastic polyurethanes, polyamides, e.g., nylon -5, nylon-12, nylon -6/6, nylon-6 /
10, fluorocarbon resins such as nylon-11, FEP, polyvinylidene fluoride, polychlorotrifluoroethylene; acrylonitrile-methyl acrylate copolymer, acrylonitrile-vinyl chloride copolymer, methacrylonitrile-styrene copolymer, polymethyl methacrylate, cellulose acetate, acetic acid Cellulose butyrate, acetal, polycarbonate, polysulfone, polyethylene oxide, polypropylene oxide, polyphenylene oxide, polyethylene and butylene terephthalate are included.

A number of thermosetting resins and crosslinkable resins are also suitable for the purposes of the present invention, including:
Radiation-cured polyethylene, peroxide-cured polyethylene, diazo-crosslinked polypropylene, epoxy resins; hydrocarbons, chloroprene and nitrile rubber, furan, melamine-formaldehyde, urea-formaldehyde, phenolformaldehyde, diallyl phthalate,
Polyester and silicone.

In one of the processes for forming this fixed bed catalyst, the binder polymer is burned off in the final product, so it is desirable to use a relatively inexpensive one for economic considerations. A preferred group of polymers are polyolefins, polyvinyl chloride, polyvinyl acetate, polystyrene and mixtures of these polymers. This polyolefin is most preferred and these are discussed separately below.

This preferred polyolefin component is, for example, (Patent Document 17) and (Patent Document 18).
) As described in the prior art mixture. Thus, this polyolefin (which may be a mixture) has a high molecular weight (at least 100,000).
0). Preferably, this is a linear polyethylene, high molecular weight polypropylene, or high molecular weight particle shape ethylene-butylene copolymer with a density of at least 0.93 to 0.97 g / cm ³ . Others are polybutenes, ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers. Useful polyolefins include a 0.0 standard load (2,160 g) melt index; a 1.8 high load (21,600 g) melt index, a density of 9.96, and 0.02 g polymer in 100 g decalin. 3. measured at 130 ° C.
It is a commercially available particle-shaped high molecular weight polyethylene having a solution viscosity of 0.

A blend of high and low molecular weight polyolefins can be used, keeping in mind that as the average molecular weight decreases, the likelihood of slumping increases during the bakeout and early part of the firing process.

When used, this plasticizer component is, for example, (Patent Document 19) and (Patent Document 2).
Can be used in prior art mixtures as described in 0)
Note that certain plasticizers, such as lower alcohols, react violently with finely ground Al and these must of course be avoided. A particularly useful plasticizer is mineral oil. Hydrocarbons (eg, low molecular weight polymers such as paraffin oil, polyisobutylene and polybutadiene) are preferred. If the removal is carried out by baking, more volatile type mineral oils are preferred.

This plasticizer enhances the processing of the composition. That is, this lowers the melt viscosity and reduces the amount of input required to incorporate and process the composition. Most importantly,
This plasticizer removes to give porosity to the composition and increases viscosity,
For firing in that it eliminates slumping during the initial part of firing, thereby retaining shape and allowing escape of residual products of polyolefin or other polymer combustion products or plasticizers from the pores Provide suitable dough.

If a plasticizer is used, this is about 10-40% by weight of the total mixture, preferably 15
Occupies -30% by weight. This is equivalent to about 0.1-0.35 cc / g, or about 30-70% by volume, preferably about 35-55% by volume.

Finely ground fillers that can be removed to enhance porosity or for other purposes can be added. For example, Al powder may be added, which is substantially removed during the elution step with NaOH. Other powdered fillers that can be removed in NaOH or other aqueous solutions are:
Includes various salts such as sugar, sodium carbonate, powdered urea and the like. Certain fillers can be added for the purpose of increasing bulk and / or strength in the final catalyst form, i.e. so that they maintain their form in use. Such fillers, TiO _2, alpha - include alumina, mullite, cordierite or the like. Everything is of course pulverized. This TiO ₂ may be expected to react with alumina during sintering to form aluminum titanate.

When processing polyolefin-containing materials, it is customary to add stabilizers (antioxidants) and lubricants. Such additives and amounts and methods of use are well known in the art.
A representative stabilizer is 4,4 thiobis (6-tert-butyl-m-cresol) ("Santon
ox ") and 2,6-di-t-butyl-4-methylphenol (" Ionol ").
The stabilizer is burned off during firing. Zinc stearate is a preferred lubricant and may be used as an auxiliary at a concentration of up to 0.5% to obtain a good dispersion of this solid in the polymer-plasticizer solution upon blending. Advantageously, other common known extrusion aids,
Stabilizers and coupling agents can be incorporated into the formulation.

In the simplest aspect, the formation of a fixed bed catalyst involves mixing only the polymer and nickel-aluminum alloy fine particles together and excluding plasticizers, fillers, and the like. The mixture is shaped and at least a portion of the Al is eluted from the mold with a NaOH solution to provide a shaped polymer bound Raney fixed bed catalyst. In another embodiment where only the polymer and alloy are used and subsequently shaped, the shaped mixture is calcined to remove the polymer, sinter the alloy particles, and then elute the Al to produce the final A calcination catalyst is formed.
(1) Mixing operation The mixing of the initial components used to form the fixed bed catalyst used herein can be carried out by any conventional means. For example, Haake rheometer, or Banb
These can be mixed using a ury or Brabender mixer.
When continuous blending is desired, it is desirable to use an interlocking twin screw blender.
Examples are from Baker Perkins Co. MP blender and Werner manufactured by
and ZSK blender manufactured by and Pfleiderer. Acceptable blends may also be produced by passing through a conventional uniaxial thermoplastic extruder many times.

In the special case of using a polyethylene / oil plasticizer, when the mixture is cooled, the oil separates as a finely dispersed liquid phase and is easily removed as described herein.

Thus, this mixture is
(A) less than minus 50 mesh, preferably about minus 100 mesh, and more preferably minus 200 mesh; about 60-90 parts by weight, preferably about 70-8.
5 parts by weight of Ni-Al alloy particles;
(B) about 1-30 parts by weight, preferably about 2-20 parts by weight of high molecular weight polymer; and (c) 0-40 parts by weight, preferably about 10-30 parts by weight, of about 0 of the total mixture. -70% by volume, preferably about 35-55% by volume, of equivalent plasticizer.
(2) Molding of mixture Next, in consideration of the geometric shape desired in the finished fixed bed catalyst, the resulting mixture is shaped into a molded product. Extrusion is one of the simplest forming methods. For example, this mixture can be extruded as a solid rod, tube (hollow or vaned) and filament with a conventional extruder, all cut into segments of the desired length in a known manner Can do. Some of the simplest and most effective excipients are 1/32, 1/16, 1 /
Pellets produced by cutting an 8 or 1/4 inch diameter rod to one-half to six times the diameter of the rod. Catalyst pellets with hollow cylinders and radial vanes may be produced by various extrusion methods. See, for example, (Patent Document 21) and (Patent Document 22) which disclose a cylindrical, hollow annular extruded product with reinforcing blades inside. Other thermoplastic molding methods such as compression and injection molding may also be used. The general idea is to mold this mixture into the final form before use (in the case of polymer-bound catalysts) or before calcination (in the case of the present calcined catalyst). Since it is easier to mold the polymer-containing mass when heated, it is preferable to heat this mixture during molding.

At this point, the material of this excipient is still identical in composition to the mixture of (1). This is the next step: ready for removal of some or all of the plasticizer (eg mineral oil).
(3) Plasticizer (oil) removal In step (2), the plasticizer can be removed from the shaped article produced by various methods. The two best methods are extraction with a solvent (eg hexane), or
If the plasticizer is sufficiently volatile (like some mineral oils), heat the mold in an air circulating oven at about 100 ° C. for several hours to evaporate and remove the oil; Specifically, the shaped product is dried. Removal of the plasticizer leaves a shaped composition consisting essentially of Raney alloy particles in the polymer matrix. That is, at this point, the composition is essentially (a) about 60-99 parts by weight of 50 mesh pass, preferably 100 mesh pass, and more preferably 200 mesh pass of US standard sieve size. , Preferably about 80-9
8 parts by weight of alloy particles;
(B) about 1-30 parts by weight, preferably about 2-20 parts by weight of high molecular weight polymer; and (c) about 0.1-70% by volume of the mixture left by removal of the plasticizer, preferably It consists of an intimate mixture of about 35-55% by volume of uniform voids.

As noted, plasticizers may be excluded from certain formulations, in which case there are of course no voids produced by the plasticizer. If a plasticizer is used, the voids occupy the same volume (or slightly less) occupied by the plasticizer.

Here, the present invention branches as described above. The next step can be to elute Al with a caustic soda solution as described in 4 below, or to calcine and then elute as described in 5 below.
(A) Elution of Al It is described that Al is partially eluted with a strong caustic soda solution (usually about 6N). Elution is carried out hot, for example at about 90 ° C, but preferably below 100 ° C. The elution with NaOH is exothermic and cold water may be added periodically to maintain the temperature at 90 ° C. The elution may require several hours and is preferably terminated with another hour of fresh sodium hydroxide solution. Next, the eluted excipient is continuously washed with water until the pH of the water drops below about 9. This result is a shaped product composed of polymer-bonded aggregates of Raney Ni fixed bed catalyst particles produced by the Raney method. These particles are still connected by the original polymer matrix. At this point, this shaped catalyst differs from the composition of (3) in that most or almost all of the Al has been removed, leaving a Raney metal.
Thus, the catalyst essentially comprises (a) particles of Raney Ni metal, about 15-50 parts by weight, preferably about 20-47 parts by weight, together with the remaining Al;
(B) about 1-30 parts by weight, preferably about 2-20 parts by weight of high molecular weight polymer; and (c) about 0.1-90%, preferably about 40-80% by volume of the total mixture. It consists of an intimate mixture of uniform voids within this mixture.

This composition has a surface area of about 20-80 m < ² > / g and a macroporosity of about 0.1-70% of the total porosity.

Several methods of elution are described by (Non-Patent Document 5). Elution with NaOH solution is preferred.

Proceed to the second alternative of calcining the composition of (3) followed by elution with sodium hydroxide.
The shaped product of calcination (3) is heated to remove the polymer, followed by calcination to melt the alloy particles into a porous metal structure. At the same time, part of this Al metal is converted to alpha-alumina. Thus, the composition is first calcined in a furnace at about 200 ° -700 ° C., preferably in the presence of air or oxygen. The temperature is increased and the calcining is completed at a temperature between 850 ° and 1200 ° C. Calcination at 900 ° C. for about 1 to 2 hours is optimal. It is meaningless to continue heating beyond 1,200 ° C.

This composition causes an increase in weight during calcination due to the conversion of some Al metal to alpha-alumina. This weight increase is typically 5-20% and is the result of an essential step in the formation of a calcined fixed bed catalyst. This alpha-alumina “spot welds” or joins (sinters) the nickel aluminum alloy particles together.

Next, the shaped fixed bed catalyst precursor calcined by the above method is exposed to alkali to remove aluminum and provide an activated fixed bed catalyst. Elution can be carried out by the method described in 4 above.

The resulting Raney Ni-Al fixed bed catalyst consists essentially of Raney Ni particles and aluminum joined together by alumina. The resulting material is extremely porous, about 20-
It has a total composition of Raney Ni that substantially forms the balance with 50 weight percent Al ₂ O ₃ . The BET surface area is usually in the range of 20 to 80 m ² / g and a pellet density (weight divided by the total pellet volume) of about 0.5-2, such as 1.1 to 1.8 g / cc, and about It has a packed bed density of 0.4 to 0.7 g / cc.

This calcined extruded or pelletized fixed bed catalyst has a structure containing macropores as well as micropores. The macropores extend over the fixed bed catalyst and are at least 60
Provides 0 angstrom porosity. This porosity is attributed to the removal of the plasticizer or combined polymer / plasticizer component from the fixed bed catalyst. Microporosity is primarily associated with voids resulting from the removal of aluminum from the precursor nickel-aluminum used to form this fixed bed catalyst. The total void volume is typically about 30 to 70 volume percent of this fixed bed catalyst pellet. The total pore volume of the Raney Ni-Al particles is
Usually about 0.3 to 0.5 cc / g.

It has been found that sulfur species can be removed therefrom by contacting the sulfur-containing hydrocarbon liquid with a Raney Ni fixed bed catalyst. Desulfurization of the liquid fraction of the fluid catalytic cracking catalyst method is particularly suitable for this method. The FCC product stream is known to contain undesired amounts of sulfur species and, therefore, if not removed, this product is not suitable for use as a fuel in light of current environmental concerns. It is. Thus, the present invention provides a means for economically, effectively and efficiently removing sulfur species from hydrocarbon liquids without adversely affecting the remaining components of the processing liquid.

This Raney Ni fixed bed catalyst may be contained in a vessel that is placed in the product stream line of a sulfur-containing liquid of an oil refining process such as an FCC unit. The fixed bed catalyst may be contained in a conventional fixed bed or moving bed reaction vessel into which the sulfur containing hydrocarbon liquid is introduced. For example, the fixed bed reactor may have the shape of a vertical cylinder, the interior of which is partitioned by a horizontal partition. While these partitions allow the liquid to be processed to pass through, Raney N
i An open or perforated plate or the like that assists in supporting and holding the fixed bed catalyst. Since this vessel is filled with a fixed bed catalyst, the liquid hits a serpentine path in the fixed bed catalyst and requires intimate contact with the Raney Ni fixed bed catalyst. Sulfur-containing liquid is typically lowered through this fixed bed catalyst bed. Typically, several fixed bed reactors are used in parallel to allow continuous desulfurization while regenerating the used fixed bed catalyst as described herein below. The resulting liquid product has been found to have a very low level of residual sulfur species, thereby providing an environmentally desirable product.

Similarly, the Raney Ni catalyst may be contacted with a sulfur containing hydrocarbon liquid used in a moving bed reaction vessel. In this case, the fixed bed catalyst and the sulfur-containing liquid are introduced into the moving bed reaction vessel. This can be done in a co-current or counter-current (preferred) manner incorporating the spent fixed bed catalyst and desulfurization liquid.

Sulfur-containing hydrocarbon liquid and Raney Ni-Al fixed bed catalyst are contacted at low temperature and pressure.
The material is contacted at a temperature in the range of about 15 ° C to 150 ° C, preferably 20-125 ° C. Pressurization (using an inert gas such as N ₂ ) from atmospheric pressure to about 0.5 to 1 mPa (5-10 atm) may be used, but the pressure at which contact is made is about 1 atm.

The method has been found to result in desulfurization of the liquid hydrocarbon feedstock without reducing the octane number of the liquid. Thus, this olefin component is not reduced to a saturated compound but causes a decrease in the octane number of the liquid.

This Raney Ni fixed bed catalyst is effective for some time, but thereafter the adsorption rate of sulfur species decreases. The exact point at which this change in speed occurs depends on the liquid hydrocarbon being treated, the amount and type of sulfur species to be adsorbed, and the type of contact used. This rate can be easily monitored as required by the method to determine when the fixed bed catalyst should be regenerated.

The regeneration of the subject Raney Ni fixed bed catalyst is
i) a used fixed bed catalyst such as hydrogen peroxide, alkali metal hypochlorite (e.g.
Mild chemistry such as NaOCl), alkali metal nitrates (eg NaNO ₃ ) or alkali metal nitrites (eg NaNO ₂ ), alkali metal perborates (eg NaBO ₃ ), peroxy acids (eg peroxyacetic acid) Treatment with an aqueous oxidant solution (this is carried out at ambient pressure and from room temperature to the boiling point of this aqueous solution, preferably from room temperature to about 10 ° C. below this boiling point, followed by water or a mild alkaline solution. Washing to remove unreacted oxidant and / or any residual sulfur oxide species);
ii) The used fixed bed catalyst is heated to 100 ° C. to 500 ° C. with hydrogen gas, preferably 200
Processing at a high temperature of ~ 400 ° C;
iii) treating the spent catalyst with a mild chemical oxidant as described herein above;
Subsequent exposure of this material to hydrogen at elevated temperatures as described hereinabove (the use of a mild oxidant alone leaves some of this catalyst in an oxidized state and therefore in a less active form, and mere treatment with hydrogen is not allowed. This method is most preferred for treating spent catalyst, as it produces bulk sulfides that are difficult to remove completely.
It has been found to reduce both concerns and produce an active catalyst substantially free of sulfur compounds); or iv) a) the organic acid is not highly reactive with Raney Ni and b ) Sulfides (MSx, in which this metal ion is insoluble in acidic solution and soluble in alkaline solution)
Where X is 1-5) and c) contacting the spent fixed bed catalyst with a metal salt of an organic acid, provided that the organic acid salt is at least partially water soluble. Can be carried out by treating the used fixed bed catalyst.

Organic acids that can be used for regeneration of the Raney nickel fixed bed catalyst are saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, isovaleric acid, etc .; saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid Succinic acid, glutaric acid, adipic acid, pimelic acid, etc .; saturated aliphatic tricarboxylic acids such as hydroxy-substituted fatty acids such as glycolic acid,
Lactic acid, gamma-hydroxybutyric acid, gluconic acid, malic acid, tartaric acid, sugar acid, citric acid, etc .;
And alicyclic acids such as cyclopentanecarboxylic acid, hexahydrobenzoic acid, hexahydrophthalic acid and the like.

After blending the spent Raney Ni fixed bed catalyst and the organic acid salt, the mixture is heated to at least about 40 ° C. and held at that temperature for a residence time of about 5 minutes. The pH of this suspension is then raised to about 6.5 to 7.1 by the addition of base. This base is preferably in the form of an aqueous solution. This temperature can be maintained at a high level during the addition. At this point, the organic acid to soluble conditions can be removed so that the insoluble metal sulfide can be removed from the catalyst-base solution mixture by decantation, filtration or some other known technique of separating the solid from the liquid. Insoluble metal sulfide formed in the processing stage. Following such a liquid removal step, the regenerated Raney nickel catalyst is preferably washed with dry alcohol to remove traces of the processing solution.

Preferred methods of reproduction are the above-mentioned methods ii) and iii), and the most preferred method is the above-mentioned method iii).

This regenerated Raney Ni fixed bed catalyst can then be used to remove sulfur species from further sulfur-containing hydrocarbon liquids. For example, if the fixed bed catalyst is used to charge a series of fixed bed reactors operated in parallel, the liquid is processed sequentially through a single or multiple reactors, while the rest of the series. Can be subjected to regeneration of the fixed bed catalyst in the manner described above. By alternating this series of reactors, one can have a continuous process that forms a substantially free hydrocarbon product that is carried out in an efficient and economical manner.

When using an ebullated bed or moving bed reactor, the spent catalyst can be regenerated outside the reactor space in one of the ways described above and then this regenerated catalyst can be fed to the reactor. it can.

It has been unexpectedly found that sulfur-containing hydrocarbon liquids such as those produced by conventional FCC processing of petroleum feeds can be easily desulfurized at low temperatures and pressure conditions. Currently required fixed bed Raney Ni catalysts effectively remove sulfur species from hydrocarbon liquids under these mild conditions, as described above. Finally, once the sulfur species absorption capacity is exhausted, the fixed bed catalyst can be easily regenerated and reused to further remove sulfur species from further sulfur-containing hydrocarbon liquids. Thus, the present invention is directed to an effective and efficient method for liquid desulfurization.

The following examples are given for illustrative purposes only and are not intended to limit the invention as defined in the appended claims. Unless otherwise noted, all parts and percentages are by weight.

Further, any number of ranges listed in the description or claims, such as those representing a particular set of properties, units of measure, conditions, physical states or percentages, etc. Any number falling within such a range, including any subset number within the range, is intended to be expressly incorporated herein by reference or otherwise.

Example 1
A series of promoted granular fixed bed catalysts were formed in the manner described below:
A. By first pulverizing the alloy with 58% by weight of Al and 42% by weight of Ni, to prepare a sample of Raney ^(R) nickel alloy. This ground material was passed through a US standard sieve No. Passing through 8 and 12 sieves, a material with a particle size of “8 × 12 mesh” was obtained. This material was converted to a useful catalyst by recycling the elution solution from the particle bed. This elution solution consisted of 5000 g of 4 weight percent sodium hydroxide,
Used to process 27 g of 8 × 12 alloy granules. The flow rate was 3.9 liters / minute. 38
This elution was carried out for 30 minutes while maintaining the temperature at ° C. Next, the pH of the effluent is less than 9.5
The catalyst was treated with 3630 g of a 3 weight percent NaOH solution and then with about 20 L of water at 38 ° C. until

Additional samples of catalyst were formed in the same manner as described above, with the following differences:
B. The initial alloy contains 4 weight percent Mo and Ni and Al are present in the same ratio as described for the alloy of Example 1;
C. 5 weight percent N further containing 0.5 weight percent ZnO dissolved in the liquid
Activation was performed with an aOH aqueous solution. The resulting catalyst contained 2.8 weight percent Zn;
D. Following activation with NaOH solution, this material is contacted with solution K ₂ ReCl ₆ to give a product having 0.2 weight percent Re; Following activation with NaOH solution, this material is contacted with solution K ₃ ReCl ₆ to give a product with 0.3 weight percent Re.

(Example 2)
A series of samples of the promoted extruded fixed bed catalyst material was formed in the manner described below:
A. The teachings are incorporated herein by reference, (Patent Document 23) and (Patent Document 2).
A mixture of 58 weight percent Al / 48 weight percent Ni alloy, polyethylene oxide polymer and glycerin as a lubricant, powdered in the same manner as described in 4) was blended. This mixture was extruded from a 1/8 inch circular cross section die head using a Haake rheometer. The polymer and lubricant were removed by heating under an inert atmosphere, and then the fixed bed catalyst precursor was calcined at 900 ° C. for 1 hour. The calcined fixed bed catalyst precursor produced was then combined with 728 g of recirculating aqueous solution with 20 percent NaOH and 90%.
This was eluted with NaOH by contact at 60 ° C. for 60 minutes. This is followed by 3640 g of a recirculating aqueous solution containing 25 weight percent NaOH and an additional 6 at 90 ° C.
Contacted for 0 minutes. Finally, the material was washed with water to obtain a pH of less than 9.5.

Additional samples were formed in the same manner as described above, with the following differences:
B. After treatment with NaOH, the fixed bed catalyst was contacted with a solution containing ammonium heptamolybdate to deposit 2.8 weight percent Mo in the resulting fixed bed catalyst product;
C. This early alloy contained 2.0 weight percent Fe metal;
D. This initial composition was extruded at 1/16 inch diameter and, after activation by contact with NaOH, an aqueous solution containing tetraammine PdCl ₂ in an amount to deposit 0.4 weight percent Pd in the final product, This material was contacted;
E. This initial composition was extruded at 1/16 inch diameter and contacted with a solution of K ₂ ReCl ₆ . The resulting material was analyzed, which was 0.1 weight percent R in the final product.
had e;
F. After activation with NaOH solution, the material was contacted with an aqueous solution containing tetraammine platinum chloride. The resulting material contained 0.03 weight percent Pt in the final product.

(Example 3)
The catalysts of Examples 1 and 2 were analyzed according to the following method:
B. E. T. T. Surface area: according to the procedure described in (Non-Patent Document 6);
CO chemisorption: calculated using the pulse method performed at 0 ° C. as described in (Non-Patent Document 6), formula: surface area (Ni) = [volume CO / g catalyst] /0.587;
Weight percent Ni: ICP-AES method after dissolving catalyst sample in acid.
By multiplying the surface area normalized by weight with the apparent bulk density (ABD) appropriate for this type of catalyst (1.8 g / cc for the granular type and 0.6 g / cc for the extruded type), B. E. T. T. And the chemisorption surface area was normalized to packed bed volume. The ABD was calculated by determining the sedimentation volume of the catalyst sample coated with water and then vacuum drying the entire sample and then weighing under an inert gas atmosphere. The weight / volume ratio is equal to ABD. This ratio varies negligibly across the different compositions used.

  The properties of Samples 1A-E and 2A-F are listed in the table below.

Example 4
The following general method was used to determine sulfur adsorption: each sample of catalyst was 0.43 under water.
"(1.1 cm) inside a vertically standing stainless steel tube filled with a piping system that pumps either gas or liquid into the catalyst bed at a controlled rate. Clamshell A resistance heating furnace was placed around the portion of the tube containing the catalyst to heat the catalyst bed during the initial drying, sulfur species adsorption, and regeneration stages.

A basic approximate adsorption / regeneration experiment was performed by first drying the catalyst sample to be tested at a high temperature of 130 ° C. in a circulating atmosphere with N ₂ alone or with H ₂ . The catalyst sample was then allowed to reach an absorption temperature as shown in each of the specific examples below while continuing the gas flow.

The catalyst packed column is then contacted with sulfur-containing gasoline at atmospheric pressure. The gasoline used was a light cut naphtha with a specific gravity of 0.73 g / cc, an analyzed total sulfur content of ˜500 ppm by weight in the gasoline range, and a boiling range of 81-437 ° F. (27-225 ° C.). .

The gasoline was passed through the column at a constant flow rate by the method of upward flow (“overflow bed”).
The spent catalyst bed is periodically purged with gasoline, and then the catalyst bed temperature is increased to 130 ° C.
Remaining by first purging the remaining gasoline with N ₂ flowing at a rate of about 1 liter / min while maintaining 0 minutes, and then the catalyst is run at a rate of about 0.5 liter / min H _{2 and} dried at 200 ° C. for 2 hours and reduced. After cooling to the outer temperature in flowing H _2, was repeated adsorption and regeneration steps. Samples of the treated gasoline are taken periodically until a predefined elapsed time at the point beyond the outlet end of this catalyst tube (for later off-line sulfur analysis),
The volume produced by this catalyst was determined.

Agilent Technologies AED detector model G2350A and Ag
GC-AED using ilent Technologies GC model 6890GC
The treated gasoline samples were analyzed for sulfur content by the method. Quantification of sulfur in the gasoline was performed according to ASTM D 5623. The value of adsorbed sulfur for each discrete time-dependent sample was calculated by subtracting the sulfur analysis concentration from the baseline sulfur analysis content of this untreated gasoline. These discrete adsorbed sulfur values were then integrated over the weight of the sent gasoline (weight = delivered volume x specific gravity) to obtain the cumulative amount of sulfur adsorbed from the gasoline during a given experiment. .

The result of the cumulative amount of sulfur adsorbed was normalized by dividing the determined result by the weight of the catalyst bed used and giving the adsorption capacity of the catalyst with the sulfur / kg catalyst. For an equivalent comparison, the cumulative gasoline volume used in the integration stage was arbitrarily set to 70 ml,
By this point, the sulfur content of the spilled gasoline has asymptotically approached the untreated baseline (
That is, almost all the capacity was used up).

Example 4-A
The granular Ni catalyst of Example 1A was charged to the reactor and contacted with gasoline generally as described above using the following specific parameters:
Adsorption temperature ~ 25 ° C (outside temperature)
0.5 ml / min gasoline flow rate (weight hourly space velocity (WHSV)) = 60 minutes × (0
. 5 ml / min) × (0.73 g / mL) /21.6 g catalyst = 1.0).

The measured sulfur capacity of this catalyst was calculated as described above and was 0.47 g sulfur / kg.
(See Tables 2 and 3 for this result and all subsequent results).

(Example 5)
Example 4-4 except that the catalyst used was the granular Mo / Ni catalyst of Example 1B
The procedure of A was followed.

(Example 6)
The procedure of Example 4-4A was followed except that the catalyst used was the extruded Mo / Ni catalyst of Example 2B.

(Example 7)
The procedure of Example 4-4A was repeated using the granular Ni catalyst of Example 1A except that 350 ° C. was used as the H ₂ reduction temperature.

(Example 8)
The procedure of Example 7 was repeated using the granular Mo / Ni catalyst of Example 1B.

Example 9
The procedure of Example 7 was repeated using the extruded Ni catalyst of Example 2A.

(Example 10)
The procedure of Example 7 was repeated using the extruded Mo / Ni catalyst of Example 2B.

(Example 11)
The procedure of Example 7 was repeated using the extruded Pd / Ni catalyst of Example 2D.

(Example 12)
The procedure of Example 7 was repeated for the granular Re / Ni catalyst of Example 2E.

(Example 13)
The adsorption step of Example 4-4A was repeated for the granular Zn / Ni catalyst of Example 1C.
No regeneration or subsequent retest was performed.

(Example 14)
The adsorption step of Example 4-4A was repeated for the granular Re / Ni catalyst of Example 1D.
No regeneration or subsequent retest was performed.

(Example 15)
The adsorption step of Example 4-4A was repeated for the granular Ru / Ni catalyst of Example 1E.
No regeneration or subsequent retest was performed.

(Example 16)
The adsorption step of Example 4-4A was repeated for the pressed Fe / Ni catalyst of Example 2C. No regeneration or subsequent retest was performed.

(Example 17)
Conducted on granular Ni catalyst of Example 1A, except that previously unused catalyst was pretreated at 200 ° C. for 2 hours in flow H ₂ and then cooled to ambient temperature prior to contact with gasoline. The adsorption step of Example 4-4A was repeated. No regeneration or subsequent retest was performed.

(Example 18)
The procedure of Example 17 was repeated for the granular Mo / Ni catalyst of Example 1B.

(Example 19)
The procedure of Example 17 was repeated for the extruded Mo / Ni catalyst of Example 2B.

(Example 20)
The procedure of Example 17 was repeated for the extruded Pd / Ni catalyst of Example 2D.

(Example 21)
The procedure of Example 17 was repeated for the extruded Pt / Ni catalyst of Example 2F.

Examples 4 to 21 above are examples 2 in which a preferred catalyst based on initial capacity was extruded.
It shows that it is a catalyst of E and that recovery of a large section of initial capacity can be achieved during regeneration using only H ₂ reduction at temperatures of about 200 ° C.-350 ° C.

(Example 22)
The procedure of Example 8 was repeated using the granular Mo / Ni catalyst of Example 1B, except that the oxidation step was performed before the H ₂ reduction step. In particular, 60 ml of 1.5% NaOCl solution was pumped into the catalyst bed at 70 ° C., followed by 60 ml of water while maintaining this temperature at 70 ° C.

(Example 23)
Example 22 except that this catalyst is the extruded Mo / Ni catalyst of Example 2B
The procedure of was repeated. The results of Example 4-23 are shown in Table 2 below.

(Example 24)
The catalyst is the granular Ni catalyst of Example 1A and the sulfur adsorption stage is 125
The procedure of Example 4-4A was repeated except that it was performed at ° C.

(Example 25)
The procedure of Example 24 was applied to the granular Ni catalyst of Example 1A, except that the H ₂ regeneration step was performed at 350 ° C.

(Example 26)
Example 25, except that the catalyst was subjected to three adsorption cycles and two cycles of regeneration.
Was applied to the granular Mo / Ni catalyst of Example 1B.

(Example 27)
The granular Mo / Ni catalyst of Example 1B was treated in the same manner as described in Example 18 in 20 H _2.
Pretreated at 0 ° C. The catalyst was subjected to absorption, oxidation and regeneration for three absorption passes.
The regeneration step was performed at 200 ° C. with H ₂ .

The results of Examples 24-27 are shown in Table 3 below. These results show that a new high capacity can be obtained for the Mo / Ni catalyst when using high temperature H ₂ pretreatment and high adsorption temperature (eg 125 ° C.).

Claims (1)

a) contacting a hydrocarbon liquid having a reduced sulfur content by contacting a sulfur-containing hydrocarbon liquid with a packed bed catalyst composition composed of a sponge nickel metal alloy at a temperature of 20 ° C. to 150 ° C. and a pressure of atmospheric pressure to 1 MPa. Generating;
b) separating and recovering the hydrocarbon liquid with reduced sulfur content;
c) regenerating the packed bed catalyst composition with hydrogen gas at a temperature of 100 ° C. to 500 ° C. to remove sulfur contained therein;
d) contacting the regenerated packed bed catalyst composition of step c) alone or with additional packed bed catalyst composition with additional sulfur-containing hydrocarbon liquid to remove sulfur therefrom; and e) step b) , C) and d) cyclically repeating the hydrocarbon liquid desulfurization method.